CN115466208B - Method for purifying spirotetramat cis-intermediate - Google Patents
Method for purifying spirotetramat cis-intermediate Download PDFInfo
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- CN115466208B CN115466208B CN202211357987.3A CN202211357987A CN115466208B CN 115466208 B CN115466208 B CN 115466208B CN 202211357987 A CN202211357987 A CN 202211357987A CN 115466208 B CN115466208 B CN 115466208B
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000005931 Spirotetramat Substances 0.000 title claims abstract description 17
- CLSVJBIHYWPGQY-GGYDESQDSA-N spirotetramat Chemical compound CCOC(=O)OC1=C(C=2C(=CC=C(C)C=2)C)C(=O)N[C@@]11CC[C@H](OC)CC1 CLSVJBIHYWPGQY-GGYDESQDSA-N 0.000 title claims abstract description 16
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 methyl 1- [2- (2, 5-dimethylphenyl) acetamido ] -4-methoxycyclohexylcarboxylate Chemical compound 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- TZIHFWKZFHZASV-UHFFFAOYSA-N anhydrous methyl formate Natural products COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 abstract description 5
- 238000006228 Dieckmann condensation reaction Methods 0.000 abstract 1
- 238000007867 post-reaction treatment Methods 0.000 abstract 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 229940091173 hydantoin Drugs 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 3
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 241000238876 Acari Species 0.000 description 1
- 238000006150 Bucherer-Bergs reaction Methods 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- PEQJBOMPGWYIRO-UHFFFAOYSA-N n-ethyl-3,4-dimethoxyaniline Chemical class CCNC1=CC=C(OC)C(OC)=C1 PEQJBOMPGWYIRO-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/54—Spiro-condensed
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for purifying spirotetramat cis-intermediate cis-3- (2, 5-dimethylphenyl) -8-methoxy-2-oxo-1-azaspiro [4,5] dec-3-en-4-ol in post-reaction treatment includes such steps as preparing cis-trans-isomer mixture of methyl 1- [2- (2, 5-dimethylphenyl) acetamido ] -4-methoxycyclohexylcarboxylate, dieckmann condensation reaction under the condition of DMF/sodium methoxide, and direct filtering to remove trans-isomer in post-treatment and filtering. The process has simple post-treatment, improves the overall yield, improves the synthesis efficiency of the spirotetramat, and has industrialized significance.
Description
Technical Field
The invention relates to the technical field of pesticide synthesis, in particular to a method for purifying a spirotetramat cis-intermediate.
Background
Spirotetramat is a novel insecticide developed by bayer corporation, belonging to the class of tetronic acid compounds. It belongs to lipid synthesis inhibitors, which by inhibiting the synthesis of insect lipids, cause death of the toxin therein. The novel pesticide and acaricide has the advantages of long lasting period, effective control of various pests and mites of the sucking mouth, upward and downward movement in the whole plant body, reaching leaf surfaces and bark, and the novel sucking performance can protect new stems, leaves and roots.
However, only cis-spirotetramat has insecticidal activity, and the trans-form of the prior national registered spirotetramat technical product needs to be controlled to be less than 2%, so that the trans-form isomer needs to be purified and controlled within a certain proportion.
In the prior patent or literature, cis-form raw materials (called hydantoin for short) are directly adoptedOr synthesizing spirotetramat by using the purified cis-form raw material or the purified cis-form raw material.
Patent CN107445883a and Shi Wenjuan et al [ pesticides (2010), 49 (4), 250-251,263] directly selected cis-8-methoxy-1, 3-diazaspiro [4,5] decane-2, 4-dione as raw material to synthesize spirotetramat. It is known from the literature that there is no natural cis-hydantoin product, the synthesis of which is produced by the Bucherer-Bergs reaction, cis: the trans ratio is about 65:35 and purification is necessary to obtain the cis-hydantoin product.
The process of example 1 in patent CN1616436a from bayer company, was purified by beating with 50% ethanol water to give cis: hydantoin products with trans=91:9 have a mass yield of 58.7%, and the pulping mode cannot control trans isomer to be less than 2%, secondary pulping is needed, and the operation difficulty is high; the procedure of example 6 gives cis by direct filtration purification: trans=99.7:0.3, the mass yield is 44.4%, the mass yield is low, and the cost is high.
The direct synthesis of spirotetramat by using a cis-trans mixture is not seen in the current patent or literature.
Disclosure of Invention
The invention aims to directly select cis-trans isomerism mixture 1- [2- (2, 5-dimethylphenyl) acetamido ] -4-methoxycyclohexyl methyl formate as a raw material aiming at the problems existing in the prior art, and provides a spirotetramat intermediate cis-3- (2, 5-dimethylphenyl) -8-methoxy-2-oxo-1-aza-spiro [4,5] dec-3-en-4-ol synthesis method capable of controlling trans isomer below 2% only by normal post-treatment and filtration operation.
In order to achieve the above purpose, the technical scheme of the invention is as follows: a method for purifying spirotetramat cis-intermediate comprises a reaction step and a post-treatment step; the reaction steps comprise:
(1) Adding metered N, N-dimethylformamide and raw material cis-trans isomerism mixture 1- [2- (2, 5-dimethyl phenyl) acetamido ] -4-methoxycyclohexyl methyl formate into a reaction vessel, stirring to dissolve the mixture;
(2) Adding metered N, N-dimethylformamide and solid sodium methoxide into another reaction container, dropwise adding N, N-dimethylformamide solution serving as a raw material at a constant temperature, and stirring at a constant temperature after the dropwise adding is finished;
the post-treatment step comprises the following steps: cooling, dropwise adding hydrochloric acid to adjust pH, adding water, stirring at room temperature, filtering, and drying, wherein the reaction formula is as follows:
After the HPLC detection reaction is completed, a post-treatment step is carried out, and the trans isomer content of the dried product detected by HPLC is less than 2%. The large amount of trans isomer was in the filtrate as detected by HPLC.
Further, the cis-trans isomerism mixture of the raw materials is 1- [2- (2, 5-dimethylphenyl) acetamido ] -4-methoxycyclohexyl methyl formate cis, trans=65-97: 35 to 3.
Further, in the reaction step (1), the mass ratio of the N, N-dimethylformamide to the raw material cis-trans isomerism mixture 1- [2- (2, 5-dimethylphenyl) acetamido ] -4-methoxycyclohexylmethyl formate is 3-4: 1.
Further, in the reaction step (2), the mass ratio of the N, N-dimethylformamide to the solid sodium methoxide is 5-6: 1.
Further, the mass ratio of the raw material cis-trans isomerism mixture 1- [2- (2, 5-dimethyl phenyl) acetamido ] -4-methoxyl cyclohexyl methyl formate to solid sodium methoxide is 2.5-3: 1.
Further, in the reaction step (2), the temperature of the N, N-dimethylformamide solution with Wen Di added raw materials is kept at 20-30 ℃ and the dripping time is 2.5-3.5 h.
Further, the temperature of the heat preservation and stirring after the completion of the dripping in the reaction step (2) is 20-30 ℃, and the heat preservation time is 1-3 h.
Further, the temperature of the post-treatment step is 0-10 ℃.
Further, the post-treatment step is carried out by dripping hydrochloric acid with the concentration of 30-35% and the pH value of 1-2.
Further, the post-treatment step comprises the following steps of raw material cis-trans isomerism mixture 1- [2- (2, 5-dimethyl phenyl) acetamido ] -4-methoxy methyl cyclohexyl formate and water in a mass ratio of 1:4 to 5.
The beneficial effects of the invention are as follows: the method for purifying the cis-intermediate cis-3- (2, 5-dimethylphenyl) -8-methoxy-2-oxo-1-aza-spiro [4,5] dec-3-en-4-ol of spirotetramat provided by the invention solves the problems of low yield and complicated post-treatment in the existing spirotetramat synthesis process, and meets the industrial production requirement. The method has novel route, low requirement on raw material configuration, simplified process, improved synthesis efficiency of spirotetramat, less than 2% of trans-intermediate product, and has industrial value.
Detailed Description
Example 1
30G of methyl 1- [2- (2, 5-dimethylphenyl) acetamido ] -4-methoxycyclohexylcarboxylate (cis: trans=65:35) were dissolved in 90g of N, N-dimethylformamide and used. 60g of N, N-dimethylformamide and 10.21g of solid sodium methoxide are sequentially added into a 500mL four-necked flask, stirring is started, and the prepared raw material solution is dropwise added after maintaining the temperature of 20-30 ℃. The reaction was continued for 1 hour at the end of the dripping. HPLC detection reaction was complete with no starting material remaining. Cooling the reaction solution to 0-10 ℃, slowly dripping 30% concentrated hydrochloric acid to adjust the pH to 1, slowly dripping 150g of water, continuously maintaining the temperature of 0-10 ℃ for stirring for 1 hour after the water dripping is finished, filtering, drying a filter cake to obtain 16.33g of a product, and detecting cis by HPLC, wherein the trans=98.2:1.8, and the mass yield is 60.21%.
1HNMR[(400MHz,DMSO-d6):10.63(s,1H),8.12(s,1H),7.08(d,1H),6.99(d,1H),6.89(s,1H),3.26(s,3H),3.16-3.10(m,1H),2.25(s,3H),2.09(s,3H),1.98-1.89(m,4H),1.56-1.51(m,2H),1.49-1.41(m,2H)].
Example 2
40G of methyl 1- [2- (2, 5-dimethylphenyl) acetamido ] -4-methoxycyclohexylcarboxylate (cis: trans=71:29) were dissolved in 120g of N, N-dimethylformamide and used. 80g of N, N-dimethylformamide and 13.61g of solid sodium methoxide are sequentially added into a 500mL four-necked flask, stirring is started, and the prepared raw material solution is dropwise added after maintaining the temperature of 20-30 ℃. The reaction was continued for 1 hour at the end of the dripping. HPLC detection reaction was complete with no starting material remaining. Cooling the reaction liquid to 0-10 ℃, slowly dripping 30% concentrated hydrochloric acid to adjust the pH to 1, slowly dripping 200g of water, continuously maintaining the temperature of 0-10 ℃ for stirring for 1 hour after the water dripping is finished, filtering, drying a filter cake to obtain 23.84g of a product, and detecting cis by HPLC, wherein the trans=98.9:1.1, and the mass yield is 65.94%.
1HNMR[(400MHz,DMSO-d6):10.63(s,1H),8.12(s,1H),7.08(d,1H),6.99(d,1H),6.89(s,1H),3.26(s,3H),3.16-3.10(m,1H),2.25(s,3H),2.09(s,3H),1.98-1.89(m,4H),1.56-1.51(m,2H),1.49-1.41(m,2H)].
Example 3
25G of methyl 1- [2- (2, 5-dimethylphenyl) acetamido ] -4-methoxycyclohexylcarboxylate (cis: trans=85:15) were dissolved in 75g of N, N-dimethylformamide for use. 50g of N, N-dimethylformamide and 8.51g of solid sodium methoxide are sequentially added into a 500mL four-necked flask, stirring is started, and the prepared raw material solution is dropwise added after maintaining the temperature of 20-30 ℃. The reaction was continued for 1 hour at the end of the dripping. HPLC detection reaction was complete with no starting material remaining. Cooling the reaction solution to 0-10 ℃, slowly dripping 30% concentrated hydrochloric acid to adjust the pH to 1, slowly dripping 125g of water, continuously maintaining the temperature of 0-10 ℃ for stirring for 1 hour after the water dripping is finished, filtering, drying a filter cake to obtain 18.35g of a product, and detecting cis by HPLC, wherein the trans=99.1:0.9, and the mass yield is 81.18%.
1HNMR[(400MHz,DMSO-d6):10.63(s,1H),8.12(s,1H),7.08(d,1H),6.99(d,1H),6.89(s,1H),3.26(s,3H),3.16-3.10(m,1H),2.25(s,3H),2.09(s,3H),1.98-1.89(m,4H),1.56-1.51(m,2H),1.49-1.41(m,2H)].
Example 4
30G of methyl 1- [2- (2, 5-dimethylphenyl) acetamido ] -4-methoxycyclohexylcarboxylate (cis: trans=97:3) were dissolved in 90g of N, N-dimethylformamide and used. 60g of N, N-dimethylformamide and 10.21g of solid sodium methoxide are sequentially added into a 500mL four-necked flask, stirring is started, and the prepared raw material solution is dropwise added after maintaining the temperature of 20-30 ℃. The reaction was continued for 1 hour at the end of the dripping. HPLC detection reaction was complete with no starting material remaining. Cooling the reaction solution to 0-10 ℃, slowly dripping 30% concentrated hydrochloric acid to adjust the pH to 1, slowly dripping 150g of water, continuously maintaining the temperature of 0-10 ℃ for stirring for 1 hour after the water dripping is finished, filtering, drying a filter cake to obtain 25.37g of a product, and detecting cis by HPLC, wherein trans=100:0, and the mass yield is 93.57%.
1HNMR[(400MHz,DMSO-d6):10.63(s,1H),8.12(s,1H),7.08(d,1H),6.99(d,1H),6.89(s,1H),3.26(s,3H),3.16-3.10(m,1H),2.25(s,3H),2.09(s,3H),1.98-1.89(m,4H),1.56-1.51(m,2H),1.49-1.41(m,2H)].
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. A method for purifying a spirotetramat cis-intermediate is characterized by comprising a reaction step and a post-treatment step; the reaction steps comprise:
(1) Adding metered N, N-dimethylformamide and raw material cis-trans isomerism mixture 1- [2- (2, 5-dimethyl phenyl) acetamido ] -4-methoxycyclohexyl methyl formate into a reaction vessel, stirring to dissolve the mixture; the cis-trans isomerism mixture of the raw materials is 1- [2- (2, 5-dimethyl phenyl) acetamido ] -4-methoxyl methyl cyclohexyl formate cis, trans=65-97: 35 to 3;
(2) Adding metered N, N-dimethylformamide and solid sodium methoxide into another reaction container, dropwise adding N, N-dimethylformamide solution serving as a raw material at a constant temperature, and stirring at a constant temperature after the dropwise adding is finished; the temperature of the N, N-dimethylformamide solution of the Wen Di added raw materials in the reaction step (2) is 20-30 ℃ and the dripping time is 2.5-3.5 h; the temperature of the reaction step (2) is kept at 20-30 ℃ after the dripping, and the heat preservation time is 1-3 h;
the post-treatment step comprises the following steps: cooling, dropwise adding hydrochloric acid to adjust pH, adding water, stirring at room temperature, filtering and drying, wherein the mass ratio of the cis-trans isomerism mixture 1- [2- (2, 5-dimethylphenyl) acetamido ] -4-methoxycyclohexyl methyl formate to water in the post-treatment step is 1:4 to 5; the reaction formula is as follows:
2. the method according to claim 1, wherein in the reaction step (1), the mass ratio of the N, N-dimethylformamide to the methyl ester of the cis-trans isomerism mixture of the raw materials 1- [2- (2, 5-dimethylphenyl) acetamido ] -4-methoxycyclohexylformate is 3-4: 1.
3. The method according to claim 1, wherein in the reaction step (2), the mass ratio of the N, N-dimethylformamide to the solid sodium methoxide is 5-6: 1.
4. The method according to claim 1, wherein the mass ratio of the raw material cis-trans isomerism mixture 1- [2- (2, 5-dimethyl phenyl) acetamido ] -4-methoxycyclohexylmethyl formate and solid sodium methoxide is 2.5-3: 1.
5. The method of claim 1, wherein the post-treatment step is carried out at a reduced temperature of from 0 ℃ to 10 ℃.
6. The method according to claim 1, wherein the post-treatment step is carried out with a drop of hydrochloric acid at a concentration of 30% to 35% and a pH of 1 to 2.
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